Development of Multifunctional Catalysts for the Direct Hydrogenation of Carbon Dioxide to Higher Alcohols.

The direct hydrogenation of greenhouse gas CO2 to higher alcohols (C2+OH) provides a new route for the production of high-value chemicals. Due to the difficulty of C-C coupling, the formation of higher alcohols is more difficult compared to that of other compounds. In this review, we summarize recent advances in the development of multifunctional catalysts, including noble metal catalysts, Co-based catalysts, Cu-based catalysts, Fe-based catalysts, and tandem catalysts for the direct hydrogenation of CO2 to higher alcohols. Possible reaction mechanisms are discussed based on the structure-activity relationship of the catalysts. The reaction-coupling strategy holds great potential to regulate the reaction network. The effects of the reaction conditions on CO2 hydrogenation are also analyzed. Finally, we discuss the challenges and potential opportunities for the further development of direct CO2 hydrogenation to higher alcohols.

Analysis of Photosynthetic Characteristics and Screening High Light-Efficiency Germplasm in Sugarcane.

Sugarcane is a globally significant crop for sugar and energy production, and developing high light-efficiency sugarcane varieties is crucial for enhancing yield and quality. However, limited research is available on the screening of sugarcane germplasm with high photosynthetic efficiency, especially with different leaf positions. The present study, conducted in Guangxi, China, aimed to analyze the photosynthetic characteristics of 258 sugarcane varieties at different leaf positions over three consecutive years in field experiments. The results showed significant differences in photosynthetic characteristics among genotypes, years, and leaf positions. Heritability estimates for various photosynthetic parameters ranged from 0.76 to 0.88. Principal component analysis revealed that the first three principal components accounted for over 99% of the cumulative variance. The first component represented photosynthetic efficiency and light utilization, the second focused on electron transfer and reaction center status, and the third was associated with chlorophyll content. Cluster and discriminant analysis classified sugarcane genotypes into three categories: high photosynthetic efficiency (HPE) with 86 genotypes, medium photosynthetic efficiency (MPE) with 60 genotypes, and low photosynthetic efficiency (LPE) with 112 genotypes. Multi-year trials confirmed that HPE sugarcane genotypes had higher single-stem weight and sucrose content. This study provides valuable insights into the photosynthetic physiological characteristics of different sugarcane varieties, which can contribute to further research regarding high yields and sugar breeding.

Dynamics of rhizosphere bacterial communities and soil physiochemical properties in response to consecutive ratooning of sugarcane.

Ratooning in sugarcane often leads to soil problems such as degradation, acidification, and soil-borne diseases that negatively impact agriculture output and sustainability. Understanding the alteration in bacterial communities, activities, and their diversity connected to the plant and soil under consecutive ratooning still needs to be clarified. To address this gap, multidisciplinary approaches such as Illumina sequencing and measurement of soil nutrients and enzymes were used in this study to analyze soil samples in a field with three consecutive ratooning sugarcane crops. The results revealed a decline in crop yield and significant changes (P < 0.05) in soil nutrients and bacterial diversity. Ratooning resulted in an acidic environment that potentially affected soil nutrients and enzyme activity responsible for the cycling of carbon, nitrogen, and phosphorous. Non-metric dimensional scaling (NMDS) confirmed the effect of ratooning on soil attributes. Moreover, a positive correlation between soil physiochemical properties and soil enzymes was observed. Alpha diversity indices indicated greater bacterial diversity in ratooning sugarcane. Bacterial diversity varied throughout the ratooning crop, and significant (P < 0.05) changes in the relative abundance of specific phyla were observed. For example, the relative abundance of Proteobacteria was decreased, and Acidobacteria was increased. Furthermore, the relative abundance of bacterial phyla was strongly correlated with soil attributes (enzymes and nutrients). Additionally, ratooning results in the depletion or enrichment of important agriculture microbial genera such as Sphingomonas, Burkholderia, and Acidothermus (P < 0.05), respectively. In conclusion, ratooning led to soil acidification, decreased fertility, and altered microbial structure and activity. Thus, restraining soil acidity by means of liming or biofertilizers to maintain soil nutrients, enzymatic activities, and microbial structure could benefit plants and soil to help create a long-term eco-friendly sugarcane cropping system.

Advances in special wettable materials for adsorption separation of high-viscosity crude oil/water mixtures.

Effective separation of highly viscous crude oil/water mixtures remains a worldwide challenge. Employing special wettable materials with adsorptive properties as an emerging separation strategy has attracted extensive attention in the treatment of crude oil spillage. Such a separation technique combines excellent wettability materials and their adsorption performance to achieve energy efficient removal or recovery of high viscosity crude oil. Particularly, special wettable adsorption materials with thermal properties provide novel ideas and directions for the construction of rapid, green, economic and all-weather crude oil/water adsorption separation materials. Negatively, the high viscosity of crude oil makes most special wettable adsorption separation materials and surfaces extremely susceptible to adhesion and contamination in practical applications, leading to rapid functional failure. Moreover, such an adsorption separation strategy towards high-viscosity crude oil/water mixture separation has rarely been summarized. Consequently, there are still some potential challenges in separation selectivity and adsorption capacity of special wettable adsorption separation materials which urgently need to be summarized to guide the future development. In this review, the special wettability theories and construction principles of adsorption separation materials are first introduced. Then, the composition and classification of crude oil/water mixtures, particularly focusing on enhancing the separation selectivity and adsorption capacity of adsorption separation materials, are comprehensively and systematically discussed via regulating surface wettability, designing pore structures and reducing crude oil viscosity. Meanwhile, the separation mechanisms, construction ideas, fabrication strategies, separation performances, practical applications, and the advantages and disadvantages of special wettable adsorption separation materials are also analyzed. Finally, the challenges and future prospects for adsorption separation of high-viscosity crude oil/water mixtures are expounded.

Characterization of a novel chitinolytic Serratia marcescens strain TC-1 with broad insecticidal spectrum.

The Gram-negative rod-shaped bacterium Serratia marcescens is an opportunistic pathogen of many organisms, including insects. We report the identification and optimal in vitro chitinase production conditions of a novel chitinolytic S. marcescens strain TC-1 isolated from a naturally infected white grub (Anomala corpulenta) collected from a peanut field at Nanyang city, Henan province, China. Strain identification was conducted by morphological, physiological, biochemical and molecular analyses. The amplified 16S rRNA gene of TC-1 showed a similarity greater than 99% with multiple strains of S. marcescens. Based on Neighbor-joining phylogenetic tree analysis of bacterial 16S rRNA gene sequences, TC-1 formed a clade with S. marcescens, clearly separated from other Serratia spp. The strain TC-1 showed larvicidal activities against five insect species (A. corpulenta, Plutella xylostella, Spodoptera exigua, Helicoverpa armigera, Bombyx mori) and the nematode Caenorhabditis elegans, but not against S. litura. The operating parameters of chitinase production by TC-1 were optimized by response surface methodology using a three-factor, three-level Box-Behnken experimental design. The effects of three independent variables i.e. colloidal chitin concentration (7-13 g l-1), incubation time (24-72 h) and incubation temperature (24-32 °C) on chitinase production by TC-1 were investigated. A regression model was proposed to correlate the independent variables for an optimal chitinase activity predicted as 20.946 U ml-1, using a combination of colloidal chitin concentration, incubation time and incubation temperature of 9.06 g l-1, 63.83 h and 28.12 °C, respectively. The latter agreed well with a mean chitinase activity of 20.761 ± 0.102 U ml-1 measured in the culture supernatants of TC-1 grown under similar conditions with a colloidal chitin concentration, incubation time and incubation temperature of 9 g l-1, 64 h and 28 °C, respectively. Our study revealed the S. marcescens strain TC-1 with potential as a biocontrol agent of insect pests and nematodes and demonstrated the proposed regression model's potential to guide chitinase production by this strain.

Preoperative prognostic nutritional index is useful factor for predicting postoperative delirium after primary total joint arthroplasty.

BACKGROUND: Postoperative delirium (PD), as an acute brain failure, is widely reported as a very common postoperative complication, and it is closely associated with increased morbidity and mortality. Recently, malnutrition is reported as one of the risk factors for PD. The prognostic nutritional index (PNI) is a simple method for nutritional evaluation. However, few studies have discussed the effectiveness of PNI as a nutritional assessment in predicting PD after primary total joint arthroplasty (TJA). The aim of this study is to investigate potential risk factors including PNI for PD following primary TJA. METHODS: A retrospective analysis of 994 patients was performed to identify risk factors associated with PD after primary TJA by using univariate and multivariate analyses. A receiver operating characteristic curve and the area under the curve were applied to evaluate the significant results of the multivariate analysis and the optimal cutoff value (CV). RESULTS: Postoperatively, sixty-seven patients (67/994, 6.7 %) experienced PD. Univariate analysis demonstrated that operative time, duration of anesthesia, age, hypertension, serum albumin, and PNI differed between the PD and non-PD groups (P < 0.05). Multivariate logistic regression analysis showed that the preoperative PNI (odds ratio [OR]: 0.908; 95 % confidence interval [CI]: 0.840-0.983; CV: 47.05), age of patients (OR: 1.055; 95 % CI: 1.024-1.087; CV: 73.5 years), and hypertension (OR: 1.798; 95 % CI: 1.047-3.086), were independently associated with PD (P < 0.05). CONCLUSIONS: A low preoperative PNI associated with malnutrition was demonstrated to be an independent risk factor for PD following primary TJA. Patients with preoperative low PNI should be cautioned and provided with adequate nutritional intervention to reduce postoperative PD.

A novel near-infrared turn-on and ratiometric fluorescent probe capable of copper(ii) ion determination in living cells.

A near-infrared ratiometric fluorescent probe CR-Ac based on a coumarin-benzopyrylium platform has been developed for selective detection of Cu2+. The cell imaging data revealed the capabilities of CR-Ac in monitoring the dynamic changes of subcellular Cu2+ and the quantification of Cu2+ levels in living cells.

Effect of the knee position during wound closure after total knee arthroplasty on early knee function recovery.

OBJECTIVE: This study investigated the effect of the knee position during wound closure on early knee function recovery after total knee arthroplasty (TKA). METHODS: This study included 80 primary total knee arthroplasties due to osteoarthritis. The patients were randomized according to the type of wound closure: extension group for full extension and flexion group for 90° flexion. The incision of articular capsule was marked for precise wound alignment. In the flexion group, the knee was kept in high flexion for 1 to 2 min after wound closure. The two groups were treated with the same postoperative rehabilitation exercises. The range of motion (ROM), visual analogue scale (VAS) score of anterior knee pain, Knee Society Score (KSS) and postoperative complications were assessed at 6 weeks, 3 months and 6 months, postoperatively. RESULTS: At 6 weeks and 3 months postoperatively, the ROM in flexion group was 98.95 ± 10.33° and 110.05 ± 4.93° respectively, with 87.62 ± 8.92° and 95.62 ± 6.51° in extension group, respectively; The VAS score of anterior knee pain in flexion group was 2.02 ± 1.38 and 2.21 ± 0.87, respectively, with 2.57 ± 1.07 and 2.87 ± 0.83 in extension group, respectively. The ROM and VAS pain score of the two groups were significantly different at these two time points, with no significant difference at 6 months postoperatively. The two groups were not significantly different in KSS, and no apparent complication was observed at three time points. CONCLUSION: Marking the articular capsule incision, wound closure in flexion and high flexion after wound closure can effectively decrease anterior knee pain after TKA and promote the early recovery of ROM.

Zinc-binding sites on selected flavonoids.

Flavonoids have attracted increased attention due to their broad bioactivities related to health and diseases. Modulating metal homeostasis may play an important role in their bioactivities. Recent studies have suggested that dietary flavonoids may affect zinc homeostasis, uptake, and transport. In this work, the zinc-binding sites on a few selected flavonoids have been investigated by (1)H NMR spectroscopy under physiological relevant pH and the species formed were verified by mass spectrometry. Zinc binding induces distinct changes in the proton resonances on the flavonoid rings, providing useful information to locate the Zn-binding sites. No Zn-binding was observed with flavone which lacks a chelation site. Zinc was found to bind to the 3-hydroxyl-4-keto, catechol, and 5-hydroxyl-4-keto chelation sites of flavonol, 3',4'-dihydroxylflavone and chrysin, respectively. Kaempferol and myricetin chelate zinc at the 3-hydroxyl-4-keto site while rutin binds zinc preferentially at the 5-hydroxyl-4-keto site. However, morin appears to bind zinc at the 1-ether-2-hydroxyl site.

Direct observation of internalization and ROS generation of amyloid ß-peptide in neuronal cells at subcellular resolution.

Seeing in many colors: Confocal images acquired using fluorescently labeled amyloid ß-peptide revealed its efficient internalization by endocytosis into endosomes/lysosomes of human neuronal cells with a small portion reaching mitochondria, inducing marked cellular and mitochondrial reactive oxygen species production.

A turn-on fluorescent sensor for imaging labile Fe(3+) in live neuronal cells at subcellular resolution.

An eye for an iron: A highly sensitive, selective and reversible turn-on Fe(3+) sensor for imaging labile Fe(3+) in live cells at subcellular resolution is reported. The sensor can respond to changes in intracellular Fe(3+) levels and was used to image endogenous chelatable Fe(3+) in live human neuroblastoma SH-SY5Y cells, with two Fe(3+) pools being identified in mitochondria and endosomes/ lysosomes for the first time.

A novel profluorescent probe for detecting oxidative stress induced by metal and H(2)O(2) in living cells.

A profluorescent probe that has no fluorescent response to H(2)O(2), iron or copper ions but can be readily activated in the presence of both H(2)O(2) and Fe (or Cu) ion has been developed; the probe is capable of detecting oxidative stress promoted by Fe (or Cu) and H(2)O(2) (i.e. the Fenton reaction conditions) in living cells.

A novel H2O2-triggered anti-Fenton fluorescent pro-chelator excitable with visible light.

A chelator and a pro-chelator that can be activated by H(2)O(2) and subsequently sequesters iron and attenuates the Fenton reaction have been developed; both molecules are fluorescent excitable by visible light, and H(2)O(2)-activation, as well as iron-chelation, induces remarkable changes in fluorescence.

Iron-binding and anti-Fenton properties of baicalein and baicalin.

Baicalein and baicalin, the major bioactive compounds found in the Chinese herb Scutellaria baicalensis, have been shown to be effective against cancer, bacterial infections and oxidative stress diseases. However, little is known about their mechanisms of action. To probe whether iron homeostasis modulation may play a role in their bioactivity, we have investigated their iron binding characteristics under physiologically relevant conditions. A 2:1 baicalein-ferrous complex was readily formed in 20mM phosphate buffer, pH 7.2, with a binding constant approximately 2-9 x 10(11)M(-2), whereas a 1:1 baicalein-ferric complex was formed, under the same conditions, with an apparent binding constant approximately 1-3 x 10(6)M(-1). Baicalein appears to bind the ferrous ion more strongly than ferrozine, a well known iron(II) chelator. Using (1) H NMR and Zn(2+) and Ga(3+) as probes, the iron-binding site on baicalein was elucidated to be at the O6/O7 oxygen atoms of the A-ring. No binding was observed for baicalin under the same NMR conditions. Furthermore, baicalein strongly inhibits the Fe-promoted Fenton chemistry via a combination of chelation and radical scavenging mechanism while baicalin can provide only partial protection against radical damage. These results indicate that baicalein is a strong iron chelator under physiological conditions and hence may play a vital role in modulating the body's iron homeostasis. Modulation of metal homeostasis and the inhibition of Fenton chemistry may be one of the possible mechanisms for herbal medicine.

Iron-binding properties of plant phenolics and cranberry's bio-effects.

The health benefits of cranberries have long been recognized. However, the mechanisms behind its function are poorly understood. We have investigated the iron-binding properties of quercetin, the major phenolic phytochemical present in cranberries, and other selected phenolic compounds (chrysin, 3-hydroxyflavone, 3',4'-dihydroxy flavone, rutin, and flavone) in aqueous media using UV/vis, NMR and EPR spectroscopies and ESI-Mass spectrometry. Strong iron-binding properties have been confirmed for the compounds containing the "iron-binding motifs" identified in their structures. The apparent binding constants are estimated to be in the range of 10(6) M(-1) to 10(12) M(-2) in phosphate buffer at pH 7.2. Surprisingly, quercetin binds Fe(2+) even stronger than the well known Fe(2+)-chelator ferrozine at pH 7.2. This may be the first example of an oxygen-based ligand displaying stronger Fe(2+)-binding affinity than a strong nitrogen-based Fe(2+)-chelator. The strong Fe-binding properties of these phenolics argue that they may be effective in modulating cellular iron homeostasis under physiological conditions. Quercetin can completely suppress Fenton chemistry both at micromolar levels and in the presence of major cellular iron chelators like ATP or citrate. However, the radical scavenging activity of quercetin provides only partial protection against Fenton chemistry-mediated damage while Fe chelation by quercetin can completely inhibit Fenton chemistry, indicating that the chelation may be key to its antioxidant activity. These results demonstrate that quercetin and other phenolic compounds can effectively modulate iron biochemistry under physiologically relevant conditions, providing insight into the mechanism of action of bio-active phenolics.

Aqua(2,2'-bi-1H-imidazole)chlorocopper(II) chloro(iminodiacetato)copper(II) monohydrate.

In the title compound, [CuCl(C6H6)N4)(H2O)][Cu(C4H5NO4)Cl].H2O, the Cu(II) atom in the cation is coordinated by one Cl- ion, two N atoms of the 2,2'-biimidazole ligand and one aqua ligand. Within the anion, the Cu(II) atom is bonded to one Cl- ion, and one N and two O atoms of the iminodiacetate ligand. Neighbouring cations and anions are connected to each other by Cu...Cl semi-coordination bonds of 2.830 (12) and 3.071 (12) A, forming a Cu2Cl2 rectangular unit. The dinuclear units further link into a polymeric chain along the a axis through Cu...O(aqua) interactions of 2.725 (3) A. Including the long coordination bonds, the geometries around the Cu atoms in the cation and anion are square-pyramidal and distorted octahedral, respectively.

Hemi[hexaaquamagnesium(II)] (mu-2,6-bis[[bis(carboxylatomethyl)amino]methyl]-4-chlorophenolato)bis[diaquamagnesium(II)] decahydrate.

The crystal structure of the title compound, [Mg(H2O)6]0.5[Mg2(C16H14ClN2O9)(H2O)4].10H2O, shows that this binuclear complex consists of two Mg centres in distorted octahedral geometry, joined by an oxo bridge which is a derivative of the deprotoned hydroxy group of the phenolate in the ligand molecule. In the anion, the coordination sphere of each MgII ion is completed by two carboxylates, a tertiary N atom and two water molecules. The inner coordination spheres for the MgII ions are very similar, both in ligand sets and in geometry. Each unit of the binuclear complex has one negative charge neutralized by a neighbouring hydrated cation, [Mg(H2O)6]2+, in which the Mg atom lies on an inversion centre. In each cell, there are 34 water molecules and most of them participate in the formation of hydrogen bonds, which contribute greatly to the stability of the whole structure.